WO2011145378A1 - Copper powder for conductive paste, and conductive paste - Google Patents
Copper powder for conductive paste, and conductive paste Download PDFInfo
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- WO2011145378A1 WO2011145378A1 PCT/JP2011/054598 JP2011054598W WO2011145378A1 WO 2011145378 A1 WO2011145378 A1 WO 2011145378A1 JP 2011054598 W JP2011054598 W JP 2011054598W WO 2011145378 A1 WO2011145378 A1 WO 2011145378A1
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- copper powder
- conductive paste
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/10—Alloys based on copper with silicon as the next major constituent
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/026—Alloys based on copper
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/10—Copper
Definitions
- the present invention relates to a copper powder for conductive paste and a conductive paste using the same. Specifically, the present invention relates to a conductive paste that can be suitably used for forming an electric circuit, forming an external electrode of a ceramic capacitor, and the like and a copper powder suitable as a conductive filler.
- the conductive paste is a fluid composition in which a conductive filler is dispersed in a vehicle composed of a resin binder and a solvent, and is widely used for forming an electric circuit, an external electrode of a ceramic capacitor, and the like.
- This type of conductive paste includes a resin-curing type in which conductive fillers are pressure-bonded by hardening of the resin to ensure conduction, and a baking type in which organic components are volatilized by baking and the conductive filler is sintered to ensure conduction. There is.
- the former resin-curable conductive paste is generally a paste-like composition containing a conductive filler made of metal powder and an organic binder made of a thermosetting resin such as an epoxy resin, and is applied with heat.
- a thermosetting resin such as an epoxy resin
- the thermosetting resin is cured and shrunk together with the conductive filler, and the conductive fillers are pressure-bonded through the resin so as to be in contact with each other, thereby ensuring conductivity.
- This resin-curable conductive paste can be processed in a relatively low temperature range from 100 ° C. to 200 ° C. and has little thermal damage, and is therefore used for printed wiring boards and heat-sensitive resin boards.
- the latter firing type conductive paste is a paste-like composition in which conductive filler (metal powder) and glass frit are generally dispersed in an organic vehicle. Conductivity is ensured by volatilization of the vehicle and further sintering of the conductive filler. At this time, the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit. Firing-type conductive paste cannot be used for printed wiring boards or resin materials because of its high firing temperature, but it can be reduced in resistance because it is sintered and the metal is integrated. It is used for external electrodes.
- Patent Document 1 proposes that a substance having a reducing action is blended in the conductive paste to suppress oxidation of the copper surface.
- Patent Document 2 proposes coating the particle surface with silver having oxidation resistance, and
- Patent Document 3 proposes coating with an inorganic oxide.
- Patent Document 4 discloses a copper alloy powder that is alloyed by adding at least one of Zn and Sn to Cu as a main component, and the content of Zn and / or Sn in the copper alloy powder is as follows.
- a copper alloy for conductive material paste is disclosed, which is 0.02 to 1.2% by mass and the copper alloy powder contains 0.005 to 0.05% by mass of P.
- Patent Document 5 discloses that the inclusion of 0.1 atm% to 10 atm% of Si in the copper powder particles can provide a good balance of conductivity while having excellent particle size and excellent oxidation resistance. ing.
- JP-A-8-73780 Japanese Patent Laid-Open No. 10-152630 JP 2005-129424 A JP 2009-99443 A JP 2010-13726 A
- the copper powder used for the baked conductive paste ensures conductivity by forming a sintered film by heating.
- the sintering temperature can be freely adjusted in the range of 500 to 900 ° C. depending on the substrate, application, paste composition and the like. Since conventional copper powder inhibits firing when copper powder is oxidized in the firing process, it is difficult to control so as to satisfy various sintering temperature characteristics required depending on the substrate, application, paste composition, etc. Was holding.
- the present invention provides a new copper powder for conductive paste and a conductive paste capable of freely controlling the sintering temperature characteristics within a range of 500 to 900 ° C. while maintaining oxidation resistance. It is in.
- the present invention is a copper powder for conductive paste containing Si (silicon) and P (phosphorus), wherein the Si concentration is 0.01 atm% or more and less than 1.2 atm%, and the Si concentration (atm%) ) And D50 ( ⁇ m) based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method, the Si equivalent amount (Si concentration ⁇ D50) is 3.50 or less.
- Si silicon
- P phosphorus
- the copper powder for conductive paste of the present invention can control the sintering temperature characteristics while maintaining oxidation resistance. That is, the product of Si concentration (atm%) and D50 ( ⁇ m) (Si concentration ⁇ D50) is defined as 3.50 or less within a Si concentration range of 0.01 atm% or more and less than 1.2 atm%.
- the sintering start temperature can be adjusted in the range of 500 to 900 ° C. Therefore, since the sintering temperature characteristics can be controlled according to the substrate, application, paste composition, etc., it is excellent as a copper powder for conductive paste.
- the present invention can be applied very well to conductive materials such as conductive pastes for various electrical contact members such as conductor circuit formation by screen printing additive method and external electrodes of multilayer ceramic capacitors.
- the copper powder for conductive paste according to the present embodiment is a copper powder for conductive paste containing Si (silicon) and P (phosphorus). Since copper powder having a composition containing Si (silicon) and P (phosphorus) may be used, metal elements other than Si (silicon) and P (phosphorus) may be contained. Typically, Cu— P-Si type copper powder.
- the feature of this copper powder is that the Si concentration is 0.01 atm% or more and less than 1.2 atm%, and the Si concentration (atm%) and the volume standard obtained by measurement by the laser diffraction scattering type particle size distribution measuring method.
- the Si equivalent amount (Si concentration ⁇ D50) calculated by the product of D50 ( ⁇ m) based on the particle size distribution is 3.50 or less.
- the sintering start temperature tends to decrease.
- the sinterability specifically, the sintering start temperature cannot be reliably controlled only by defining either the Si (silicon) concentration or the particle size. Therefore, when the product of both, that is, the product of Si concentration and D50 (Si concentration ⁇ D50) was studied as a reference value, it was found that the sintering start temperature could be controlled stepwise at least when the Si concentration was within a certain range. I was able to.
- the Si concentration x D50 of the copper powder is 3.50 or less, preferably 0.001 to 3.40, particularly 0.005 to 3.00, and particularly 0.01 It is even better to be up to 2.80.
- Such copper powder can be manufactured by adjusting the atomizing conditions based on the examples, as will be described later in the item of the manufacturing method. However, it is not limited to this method.
- the copper powder particle (referred to as “the present copper powder particle”) having Si concentrated on the surface is the main material, 100% of all the copper powder particles are concentrated on the surface. It can be considered that the same effect can be obtained even if the copper powder particles are not present. Therefore, in this copper powder, it is preferable that the copper powder particle
- a method of adjusting the atomizing conditions based on the examples can be mentioned as described in the item of the manufacturing method later. However, it is not limited to this method.
- the Si concentration of the copper powder particles is in the range of 0.01 atm% or more and less than 1.2 atm%.
- the sintering start temperature can be more preferably adjusted in the range of 500 to 900 ° C. while maintaining oxidation resistance.
- the Si concentration of the present copper powder particles is preferably in the range of 0.01 atm% or more and less than 1.0 atm%, and particularly 0.03 atm%. Above all, 0.05 atm% or more, or particularly less than 0.2 atm%, especially less than 0.1 atm% is even more preferable.
- the P (phosphorus) concentration of the copper powder particles is not particularly limited, but the P (phosphorus) content is 0.01 to 0.3 atm%, particularly 0.02 atm% or more, or 0.1 atm%. In the following, it is preferable to contain at a ratio of 0.02 atm% or more or 0.06 atm% or less. If P (phosphorus) is contained in such a range, it has fine particle size and oxidation resistance, does not impair electrical conductivity, has small variations in shape and particle size, and can reduce oxygen concentration. From this viewpoint, the present copper powder particles more preferably contain P (phosphorus) in the particles at a ratio of 0.02 atm% or more and 0.04 atm% or less.
- the copper powder particles preferably have a granular shape, particularly a spherical shape.
- granular means a shape in which the aspect ratio (value obtained by dividing the average major axis by the average minor axis) is about 1 to 1.25, and the aspect ratio is about 1 to 1.1. Is called spherical.
- a state where the shapes are not aligned is called an indefinite shape.
- Such a granular copper powder is very preferable because it causes less mutual entanglement and improves dispersibility in the paste when used as a conductive material for a conductive paste.
- D50 based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method is defined by the Si concentration and the value of Si concentration ⁇ D50.
- the thickness is preferably 1 ⁇ m to 10 ⁇ m.
- the sintering start temperature can be more preferably adjusted within the range of 500 to 900 ° C. while maintaining oxidation resistance.
- the D50 of the present copper powder particles is preferably 0.1 ⁇ m to 10 ⁇ m, particularly 0.3 ⁇ m or more, or 5 ⁇ m or less, especially 0.5 ⁇ m or more. Or it is still more preferable that it is 3 micrometers or less.
- the (initial) oxygen concentration of the copper powder is preferably 800 ppm to 5000 ppm.
- the oxygen concentration is within such a range, the conductivity and oxidation resistance as the conductive material of the conductive paste can be made good.
- the copper powder particles are concentrated on the surface of the copper powder particles, a thin film of silicon oxide is formed on the entire surface of the copper powder particles, and it is difficult for oxygen to enter the particles. Even if the initial oxygen concentration is relatively high, it can be considered that the oxidation resistance can be satisfactorily maintained by the silicon oxide film on the surface.
- the (initial) oxygen concentration of the copper powder is preferably 800 ppm to 5000 ppm, more preferably 1000 ppm or more, or 4000 ppm or less, and particularly preferably 1200 ppm or more, or 3000 ppm or less.
- the sintering start temperature of the copper powder is preferably 500 to 900 ° C. If the sintering start temperature can be adjusted within such a temperature range, the sintering temperature characteristics can be controlled according to the substrate, application, paste composition, etc., which is very convenient.
- the present copper powder is, for example, Ni, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, In, Zr, Nb, B, Ge, You may contain at least 1 type or more of element components among Sn, Zn, Bi, etc. By adding these, it is possible to adjust various characteristics required for the conductive paste, for example, to improve the sinterability by lowering the melting point.
- This copper powder can be produced by adding a predetermined amount of Si component and other additive element components in the form of a mother alloy or a compound to molten copper and then pulverizing it by a predetermined atomization method. it can.
- This type of copper powder can be applied to a wet reduction method in which a copper salt-containing solution or the like is deposited with a reducing agent, a vapor phase reduction method in which the copper salt is heated and vaporized and reduced in the gas phase, or a molten copper ingot. It can be produced by an atomizing method in which it is rapidly cooled with a refrigerant such as active gas or water to form a powder.
- the atomization method can reduce the residual concentration of impurities in the obtained copper powder as compared with the wet reduction method that is generally widely used, and also from the surface of the obtained copper powder particles. This has the advantage that the number of pores reaching the inside can be reduced. For this reason, the copper powder produced by the atomization method has the advantage that, when used as a conductive material of a conductive paste, the amount of gas generated during paste curing can be reduced and the progress of oxidation can be greatly suppressed. Yes.
- the water atomizing method can be preferably employed.
- water atomization not only can the Si be more effectively concentrated on the particle surface, but also the particles can be made finer.
- dissolved oxygen in water is taken into the particles, so that a tendency to increase the oxygen concentration is recognized.
- the high pressure atomizing method is preferable because the particles can be produced finely and uniformly.
- the high pressure atomizing method is a method of atomizing at a water pressure of about 50 MPa to 150 MPa in the water atomizing method.
- the copper powder obtained by atomization may be reduced.
- the reduction treatment it is possible to further reduce the oxygen concentration on the surface of the copper powder that is easily oxidized.
- the reducing gas is not particularly limited, and examples thereof include hydrogen gas, ammonia gas, and butane gas.
- the reduction treatment is preferably performed at a temperature of 150 to 300 ° C., more preferably at a temperature of 170 to 210 ° C. This is because if the temperature is less than 150 ° C., the reduction rate becomes slow, and the treatment effect cannot be sufficiently exhibited, and if the temperature exceeds 300 ° C., it causes aggregation and sintering of copper powder. This is because when the temperature is 170 ° C. to 210 ° C., aggregation and sintering of copper powder can be reliably suppressed while efficiently reducing the oxygen concentration.
- the powdered copper powder is preferably classified. This classification can be easily carried out by separating coarse powder and fine powder using an appropriate classifier so that the target particle size is at the center.
- this copper powder can be used as it is, it can also be used after the copper powder is subjected to shape processing.
- a spherical particle powder (powder consisting of 80% or more of spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (: 80% or more of non-spherical particles) Powder).
- flaky particle powder (: 80% or more from flaky particles) is mechanically flattened (rolled or stretched) using a bead mill, ball mill, attritor, vibration mill or the like. Shape powder).
- a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
- an auxiliary agent such as a surfactant.
- the copper powder which carried out such shape processing can also be utilized, and the original powder which is not shape-processed and this can also be mixed and utilized.
- the copper powder is suitable as a conductive filler used for, for example, any of a resin curable conductive paste and a fired conductive paste. Therefore, for example, the present copper powder can be blended with an organic binder made of a thermosetting resin such as an epoxy resin to prepare a resin curable conductive paste, or the present copper powder can be blended into an organic vehicle. A fired conductive paste can also be prepared.
- Copper powder for conductive paste using this copper powder as a conductive filler is suitable as a conductive paste for various electrical contact members such as for forming conductive circuits by screen printing additive method and for external electrodes of multilayer ceramic capacitors. Can be used for
- the copper powder for conductive paste of the present invention is used for internal electrodes of multilayer ceramic capacitors, chip parts such as inductors and resistors, single plate capacitor electrodes, tantalum capacitor electrodes, resin multilayer substrates, ceramic (LTCC) multilayer substrates, flexible Printed circuit boards (FPC), antenna switch modules, modules such as PA modules and high-frequency active filters, PDP front and back plates, electromagnetic shielding films for PDP color filters, crystalline solar cell surface electrodes and rear lead electrodes, conductive adhesives It can also be used for membrane switches such as EMI shield, RF-ID, and PC keyboard, anisotropic conductive film (ACF / ACP), and the like.
- chip parts such as inductors and resistors, single plate capacitor electrodes, tantalum capacitor electrodes, resin multilayer substrates, ceramic (LTCC) multilayer substrates, flexible Printed circuit boards (FPC), antenna switch modules, modules such as PA modules and high-frequency active filters, PDP front and back plates, electromagnetic shielding films for PDP color filters, crystalline solar
- the oxygen concentration (also referred to as initial oxygen concentration) of the copper powder (sample) was analyzed using an oxygen / nitrogen analyzer (“EMGA-520 (model number)” manufactured by Horiba, Ltd.).
- the sintering start temperature was examined using TMA / SS6000 which is a thermomechanical analyzer (TMA apparatus) manufactured by Seiko Instruments Inc.
- TMA / SS6000 thermomechanical analyzer
- sintering is delayed more appropriately than copper containing P (phosphorus), that is, the sintering start temperature is more appropriate than the sintering start temperature (around 490 ° C.) of copper containing P (phosphorus).
- the “evaluation of sinterability” in this example is “ ⁇ ” in the range of 500 to 900 ° C., particularly “ ⁇ ” in the range of 500 to 550 ° C. in the low temperature region, and 500 to 900.
- the thing outside the range of ° C. was evaluated as “x”.
- Example preparation Examples and Comparative Examples> 100 kg of molten copper (copper purity: Cu 99.95%) melted (1350 ° C) with Si as a pure metal and further a copper-phosphorus mother alloy (P15 wt%) mixed thoroughly and mixed. A molten metal was prepared. Next, 100 kg of the molten metal was poured into the tundish in the water atomizer (holding temperature 1300 ° C.), and the molten metal was dropped from the nozzle (caliber 5 mm) at the bottom of the tundish (flow rate 5 kg / min).
- Copper powder was manufactured by jetting water (water pressure: 100 MPa, water amount: 350 L / min) into the molten metal so as to form an inverted conical water flow shape from an injection hole having a diameter of 26 mm). Next, the obtained copper powder was classified by a classifier (“Turbo Classifier (trade name) TC-25 (model number)” manufactured by Nissin Engineering Co., Ltd.) to obtain a copper powder (sample).
- a classifier “Turbo Classifier (trade name) TC-25 (model number)” manufactured by Nissin Engineering Co., Ltd.
- Example 6-7 the copper powder obtained by water atomization was classified by a classifier (“Turbo Classifier (trade name) TC-25 (model number)” manufactured by Nissin Engineering Co., Ltd.). The obtained copper powder was mechanically flattened using a bead mill.
- a classifier Teurbo Classifier (trade name) TC-25 (model number) manufactured by Nissin Engineering Co., Ltd.
- Example 1-5 As a result of observing and analyzing the copper powder obtained in Example 1-5 with an electron microscope or the like, most of them were spherical particles, and compared with the Si concentration at a depth of 10 nm from the surface of the copper powder particles, the depth at a depth of 2 nm from the surface. It was found that the Si concentration was high and Si was concentrated in the surface layer. Moreover, as a result of observing and analyzing the copper powder obtained in Example 6-7 with an electron microscope or the like, most were flaky particles, and the depth from the surface was larger than the Si concentration at a depth of 10 nm from the surface of the copper powder particles. It was found that the Si concentration at 2 nm was high, and Si was concentrated in the surface layer.
- the Si (silicon) concentration is in the range of 0.01 atm% or more and less than 1.2 atm%, There was a tendency to increase the sintering start temperature by increasing the Si concentration.
- the Si (silicon) concentration is preferably less than 0.10 atm% from this viewpoint.
- the sintering start temperature tends to decrease.
- the sintering start temperature cannot be controlled only by defining either the Si (silicon) concentration or the particle size.
- the Si concentration x D50 of the copper powder is 3.50 or less, preferably 0.001 to 3.40, particularly 0.005 to 3.00, and particularly 0.01 It can be considered that ⁇ 2.80 is even better.
- the sintering temperature characteristic can be controlled like the copper powder of this example, although it is not necessarily confirmed experimentally, a small amount of Si (silicon) present on the surface of the copper powder particles is present.
- the oxide component that is, the ceramic component can be segregated, and it can be considered that the sintering temperature characteristics can be changed depending on the degree of segregation.
- the oxide component segregates at the grain boundary after sintering, it is excellent in that it does not hinder the conductivity.
- the value of Si concentration ⁇ D50 is changed by fixing D50 and changing the Si concentration.
- the value of Si concentration ⁇ D50 is changed by changing D50 in the range of about 0.1 ⁇ m to 10 ⁇ m. The same effect can be obtained even if the value is changed. Further, it has been confirmed that such an effect is not influenced by the P (phosphorus) concentration. Since the P (phosphorus) concentration affects the micronization and oxidation resistance, it can be considered that the P (phosphorus) content is preferably 0.01 to 0.3 atm%.
Abstract
Description
焼成型導電性ペーストは、焼成温度が高いため、プリント配線基板や樹脂材料には使用できないが、焼結して金属が一体化することから低抵抗化を実現することができ、例えば積層セラミックコンデンサの外部電極などに使用されている。 On the other hand, the latter firing type conductive paste is a paste-like composition in which conductive filler (metal powder) and glass frit are generally dispersed in an organic vehicle. Conductivity is ensured by volatilization of the vehicle and further sintering of the conductive filler. At this time, the glass frit has a function of adhering the conductive film to the substrate, and the organic vehicle functions as an organic liquid medium for enabling printing of the metal powder and the glass frit.
Firing-type conductive paste cannot be used for printed wiring boards or resin materials because of its high firing temperature, but it can be reduced in resistance because it is sintered and the metal is integrated. It is used for external electrodes.
そこで、導電性ペーストに用いる銅粉に関しては、従来から、銅粉表面の酸化を防止する方法が種々提案されている。 In both the resin curable conductive paste and the high-temperature fired conductive paste, silver powder has been conventionally used as a conductive filler, but it is cheaper to use copper powder and migration is less likely to occur. Since the soldering resistance is also excellent, conductive paste using copper powder is being widely used. However, copper powder easily oxidizes in the air, and the oxide film on the surface of the copper powder has a problem of increasing the connection resistance.
Therefore, various methods for preventing oxidation of the copper powder surface have been conventionally proposed for the copper powder used in the conductive paste.
また、特許文献2では、粒子表面を耐酸化性のある銀でコートすることが提案され、特許文献3では、無機酸化物でコートすることが提案されている。 For example, Patent Document 1 proposes that a substance having a reducing action is blended in the conductive paste to suppress oxidation of the copper surface.
Patent Document 2 proposes coating the particle surface with silver having oxidation resistance, and Patent Document 3 proposes coating with an inorganic oxide.
従来の銅粉は、焼成工程で銅粉が酸化すると焼成を阻害するため、基板、用途、ペーストの配合組成などにより様々に求められる焼結温度特性を満足するようにコントロールすることが難しいという課題を抱えていた。 The copper powder used for the baked conductive paste ensures conductivity by forming a sintered film by heating. Ideally, the sintering temperature can be freely adjusted in the range of 500 to 900 ° C. depending on the substrate, application, paste composition and the like.
Since conventional copper powder inhibits firing when copper powder is oxidized in the firing process, it is difficult to control so as to satisfy various sintering temperature characteristics required depending on the substrate, application, paste composition, etc. Was holding.
本実施形態に係る導電性ペースト用銅粉(以下、「本銅粉」と称する)は、Si(ケイ素)及びP(リン)を含有する導電性ペースト用銅粉である。Si(ケイ素)及びP(リン)を含有する組成の銅粉であればよいから、Si(ケイ素)及びP(リン)以外の金属元素を含有していてもよいが、典型的にはCu-P-Si型銅粉である。 <Copper powder for conductive paste>
The copper powder for conductive paste according to the present embodiment (hereinafter referred to as “the present copper powder”) is a copper powder for conductive paste containing Si (silicon) and P (phosphorus). Since copper powder having a composition containing Si (silicon) and P (phosphorus) may be used, metal elements other than Si (silicon) and P (phosphorus) may be contained. Typically, Cu— P-Si type copper powder.
P(リン)を含有する銅粉にSi(ケイ素)を添加すると、Si(ケイ素)濃度0.01atm%以上1.2atm%未満の範囲内であれば、Si濃度を高めることにより焼結開始温度を高くすることができる傾向があることを見出すことができた。また、粒径が小さければ、焼結開始温度が低下する傾向があることも確認することができた。しかし、Si(ケイ素)濃度と粒径の何れかを規定するだけでは、焼結性、具体的には焼結開始温度を確実に制御できないことも確認された。そこで、両者の積、すなわち、Si濃度とD50の積(Si濃度×D50)を基準値として検討したところ、少なくもSi濃度が一定範囲内においては焼結開始温度を段階的に制御できることを見出すことができた。
かかる観点から、本銅粉のSi濃度×D50は、3.50以下であることが重要であり、好ましくは0.001~3.40、特に0.005~3.00、中でも特に0.01~2.80であるのがさらによい。
このような銅粉は、後の製造方法の項目において説明するように、実施例に基づいてアトマイズ条件を調整することにより製造することができる。但し、この方法に限定するものではない。 The feature of this copper powder is that the Si concentration is 0.01 atm% or more and less than 1.2 atm%, and the Si concentration (atm%) and the volume standard obtained by measurement by the laser diffraction scattering type particle size distribution measuring method. The Si equivalent amount (Si concentration × D50) calculated by the product of D50 (μm) based on the particle size distribution is 3.50 or less.
When Si (silicon) is added to copper powder containing P (phosphorus), if the Si (silicon) concentration is in the range of 0.01 atm% or more and less than 1.2 atm%, the sintering start temperature is increased by increasing the Si concentration. I found out that there is a tendency to be high. It was also confirmed that if the particle size is small, the sintering start temperature tends to decrease. However, it has also been confirmed that the sinterability, specifically, the sintering start temperature cannot be reliably controlled only by defining either the Si (silicon) concentration or the particle size. Therefore, when the product of both, that is, the product of Si concentration and D50 (Si concentration × D50) was studied as a reference value, it was found that the sintering start temperature could be controlled stepwise at least when the Si concentration was within a certain range. I was able to.
From this viewpoint, it is important that the Si concentration x D50 of the copper powder is 3.50 or less, preferably 0.001 to 3.40, particularly 0.005 to 3.00, and particularly 0.01 It is even better to be up to 2.80.
Such copper powder can be manufactured by adjusting the atomizing conditions based on the examples, as will be described later in the item of the manufacturing method. However, it is not limited to this method.
Si濃度が極めて低いために定量的に分析することは難しいが、銅粉粒子全体の表面に酸化ケイ素の薄い膜ができるため、内部に酸素が入り難くなり、その結果として焼結性を高めることができ、しかも、耐酸化性も高くなるのではないかと推察することができる。
なお、本銅粉において、表面にSiが濃化している銅粉粒子(「本銅粉粒子」と称する)が主材料であれば、100%全ての銅粉粒子が表面にSiが濃化している銅粉粒子でなくても、同様の効果が得られると考えることができる。よって、本銅粉においては、表面にSiが濃化している銅粉粒子が全体の50wt%以上、好ましくは80wt%以上、特に90wt%以上(100wt%を含む)を占めるのが好ましい。
このように銅粉粒子の表面にSiを濃化させるためには、後の製造方法の項目において説明するように、実施例に基づいてアトマイズ条件を調整する方法を挙げることができる。但し、この方法に限定するものではない。 As a result of analyzing this copper powder, that is, a copper powder having a Si concentration × D50 of 3.50 or less, it was found that Si was concentrated on the surface of the copper powder particles. As a more specific measure, it was confirmed that the Si concentration at a depth of 2 nm from the surface was higher than the Si concentration at a depth of 10 nm from the surface of the copper powder particles.
Although it is difficult to analyze quantitatively because the Si concentration is extremely low, a thin film of silicon oxide is formed on the entire surface of the copper powder particles, making it difficult for oxygen to enter inside, and as a result, improving the sinterability In addition, it can be inferred that the oxidation resistance may be increased.
In addition, in this copper powder, if the copper powder particle (referred to as “the present copper powder particle”) having Si concentrated on the surface is the main material, 100% of all the copper powder particles are concentrated on the surface. It can be considered that the same effect can be obtained even if the copper powder particles are not present. Therefore, in this copper powder, it is preferable that the copper powder particle | grains with which Si is concentrated on the surface occupy 50 wt% or more of the whole, Preferably it is 80 wt% or more, Especially 90 wt% or more (100 wt% is included).
In order to concentrate Si on the surface of the copper powder particles as described above, a method of adjusting the atomizing conditions based on the examples can be mentioned as described in the item of the manufacturing method later. However, it is not limited to this method.
このように耐酸化性維持と焼結開始温度の制御の観点から、本銅粉粒子のSi濃度は、0.01atm%以上1.0atm%未満の範囲であるのが好ましく、特に0.03atm%以上、中でも0.05atm%以上、或いは、特に0.2atm%未満、中でも0.1atm%未満であるのがより一層好ましい。 It is important that the Si concentration of the copper powder particles is in the range of 0.01 atm% or more and less than 1.2 atm%. By adjusting the Si concentration in such a range, the sintering start temperature can be more preferably adjusted in the range of 500 to 900 ° C. while maintaining oxidation resistance.
Thus, from the viewpoint of maintaining oxidation resistance and controlling the sintering start temperature, the Si concentration of the present copper powder particles is preferably in the range of 0.01 atm% or more and less than 1.0 atm%, and particularly 0.03 atm%. Above all, 0.05 atm% or more, or particularly less than 0.2 atm%, especially less than 0.1 atm% is even more preferable.
このような範囲でP(りん)を含有すれば、粒度微細、耐酸化性を有し、導電性を損なわず、形状や粒度のバラツキが小さく、酸素濃度を低くすることができる。
かかる観点から、本銅粉粒子は、粒子内部にP(りん)を0.02atm%以上、0.04atm%以下の割合で含有するのがより一層好ましい。 The P (phosphorus) concentration of the copper powder particles is not particularly limited, but the P (phosphorus) content is 0.01 to 0.3 atm%, particularly 0.02 atm% or more, or 0.1 atm%. In the following, it is preferable to contain at a ratio of 0.02 atm% or more or 0.06 atm% or less.
If P (phosphorus) is contained in such a range, it has fine particle size and oxidation resistance, does not impair electrical conductivity, has small variations in shape and particle size, and can reduce oxygen concentration.
From this viewpoint, the present copper powder particles more preferably contain P (phosphorus) in the particles at a ratio of 0.02 atm% or more and 0.04 atm% or less.
かかる範囲でD50を調整することにより、耐酸化性を維持しつつ焼結開始温度を500~900℃の範囲でより好ましく調整することができる。
耐酸化性維持と焼結開始温度の制御の観点から、本銅粉粒子のD50は、0.1μm~10μmであるのが好ましく、特に0.3μm以上、或いは5μm以下、中でも0.5μm以上、或いは、3μm以下であるのがより一層好ましい。 In the present copper powder, D50 based on the volume-based particle size distribution obtained by measurement by the laser diffraction / scattering particle size distribution measurement method is defined by the Si concentration and the value of Si concentration × D50. The thickness is preferably 1 μm to 10 μm.
By adjusting D50 within such a range, the sintering start temperature can be more preferably adjusted within the range of 500 to 900 ° C. while maintaining oxidation resistance.
From the viewpoint of maintaining the oxidation resistance and controlling the sintering start temperature, the D50 of the present copper powder particles is preferably 0.1 μm to 10 μm, particularly 0.3 μm or more, or 5 μm or less, especially 0.5 μm or more. Or it is still more preferable that it is 3 micrometers or less.
本銅粉粒子は、上述のように、銅粉粒子の表面にSiが濃化しており、銅粉粒子全体の表面に酸化ケイ素の薄い膜ができており、粒子内部に酸素が入り難いため、初期酸素濃度が比較的高くても、表面の酸化ケイ素被膜によって耐酸化性を良好に維持することができるものと考えることができる。
かかる観点から、本銅粉の(初期)酸素濃度は800ppm~5000ppmであるのが好ましく、特に1000ppm以上、或いは4000ppm以下、中でも特に1200ppm以上、或いは3000ppm以下であるのがさらに好ましい。 The (initial) oxygen concentration of the copper powder is preferably 800 ppm to 5000 ppm. When the oxygen concentration is within such a range, the conductivity and oxidation resistance as the conductive material of the conductive paste can be made good.
As described above, the copper powder particles are concentrated on the surface of the copper powder particles, a thin film of silicon oxide is formed on the entire surface of the copper powder particles, and it is difficult for oxygen to enter the particles. Even if the initial oxygen concentration is relatively high, it can be considered that the oxidation resistance can be satisfactorily maintained by the silicon oxide film on the surface.
From this viewpoint, the (initial) oxygen concentration of the copper powder is preferably 800 ppm to 5000 ppm, more preferably 1000 ppm or more, or 4000 ppm or less, and particularly preferably 1200 ppm or more, or 3000 ppm or less.
これらを添加することにより、例えば融点を低下させて焼結性を向上させるなど、導電性ペーストに求められる諸特性を調整することができる。 In addition to Si (silicon) and P (phosphorus), the present copper powder is, for example, Ni, Ti, Fe, Co, Cr, Mg, Mn, Mo, W, Ta, In, Zr, Nb, B, Ge, You may contain at least 1 type or more of element components among Sn, Zn, Bi, etc.
By adding these, it is possible to adjust various characteristics required for the conductive paste, for example, to improve the sinterability by lowering the melting point.
次に、本銅粉の好ましい具体的な製造方法について説明する。 <Production method>
Next, the preferable specific manufacturing method of this copper powder is demonstrated.
この種の銅粉は、銅塩を含む溶液などから還元剤により析出させる湿式還元法や、銅塩を加熱気化させて気相中で還元させる気相還元法や、溶融した銅地金を不活性ガスや水等の冷媒で急冷して粉末化するアトマイズ法などにより、製造することが可能である。これらの中でアトマイズ法は、一般的に広く利用されている湿式還元法に比べて、得られる銅粉中の不純物の残留濃度を小さくすることができると共に、得られる銅粉の粒子の表面から内部に至る細孔を少なくすることができるという利点を有している。このため、アトマイズ法により製造された銅粉は、導電性ペーストの導電材料に使用した場合、ペースト硬化時のガス発生量を少なくできると共に、酸化の進行を大幅に抑制できるという利点を有している。 This copper powder can be produced by adding a predetermined amount of Si component and other additive element components in the form of a mother alloy or a compound to molten copper and then pulverizing it by a predetermined atomization method. it can.
This type of copper powder can be applied to a wet reduction method in which a copper salt-containing solution or the like is deposited with a reducing agent, a vapor phase reduction method in which the copper salt is heated and vaporized and reduced in the gas phase, or a molten copper ingot. It can be produced by an atomizing method in which it is rapidly cooled with a refrigerant such as active gas or water to form a powder. Among these, the atomization method can reduce the residual concentration of impurities in the obtained copper powder as compared with the wet reduction method that is generally widely used, and also from the surface of the obtained copper powder particles. This has the advantage that the number of pores reaching the inside can be reduced. For this reason, the copper powder produced by the atomization method has the advantage that, when used as a conductive material of a conductive paste, the amount of gas generated during paste curing can be reduced and the progress of oxidation can be greatly suppressed. Yes.
高圧アトマイズ法とは、水アトマイズ法においては、50MPa~150MPa程度の水圧力でアトマイズする方法である。 Among the water atomizing methods, the high pressure atomizing method is preferable because the particles can be produced finely and uniformly.
The high pressure atomizing method is a method of atomizing at a water pressure of about 50 MPa to 150 MPa in the water atomizing method.
上記還元処理は、150~300℃の温度で行うのが好ましく、特に170~210℃の温度で行うとより好ましい。なぜなら、上記温度が150℃未満であると、還元速度が遅くなってしまい、処理効果を充分に発現することができず、上記温度が300℃を超えると、銅粉の凝集や焼結を引き起こしてしまうおそれがあり、上記温度が170℃~210℃であると、酸素濃度の効率のよい低減化を図りながらも、銅粉の凝集や焼結を確実に抑制することができるからである。 As such a reduction treatment, reduction with a gas is preferable from the viewpoint of workability. The reducing gas is not particularly limited, and examples thereof include hydrogen gas, ammonia gas, and butane gas.
The reduction treatment is preferably performed at a temperature of 150 to 300 ° C., more preferably at a temperature of 170 to 210 ° C. This is because if the temperature is less than 150 ° C., the reduction rate becomes slow, and the treatment effect cannot be sufficiently exhibited, and if the temperature exceeds 300 ° C., it causes aggregation and sintering of copper powder. This is because when the temperature is 170 ° C. to 210 ° C., aggregation and sintering of copper powder can be reliably suppressed while efficiently reducing the oxygen concentration.
この分級は、適切な分級装置を用いて、目的とする粒度が中心となるように、粗粉や微粉を分離することにより容易に実施することができる。 The powdered copper powder is preferably classified.
This classification can be easily carried out by separating coarse powder and fine powder using an appropriate classifier so that the target particle size is at the center.
本銅粉は、そのまま利用することも可能であるが、本銅粉を形状加工処理した上で、利用することもできる。
例えば、球状粒子粉末(:80%以上が球状粒子からなる粉末)を、機械的に形状加工して、フレーク状、鱗片状、平板状などの非球状粒子粉末(:80%以上が非球状粒子からなる粉末)に加工することができる。
より具体的には、ビーズミル、ボールミル、アトライター、振動ミルなどを用いて機械的に偏平化加工(圧伸延または展伸)することにより、フレーク状粒子粉末(:80%以上がフレーク状粒子からなる粉末)に形状加工することができる。この際、粒子同士の凝集や結合を防止しながら各粒子を独立した状態で加工するために、例えばステアリン酸などの脂肪酸や、界面活性剤などの助剤を添加するのが好ましい。
そして、このような形状加工処理した銅粉を利用することもできるし、また、形状加工しない元粉とこれとを混合して利用することもできる。 (Shape processing)
Although this copper powder can be used as it is, it can also be used after the copper powder is subjected to shape processing.
For example, a spherical particle powder (powder consisting of 80% or more of spherical particles) is mechanically processed into non-spherical particle powders such as flakes, scales, and flat plates (: 80% or more of non-spherical particles) Powder).
More specifically, flaky particle powder (: 80% or more from flaky particles) is mechanically flattened (rolled or stretched) using a bead mill, ball mill, attritor, vibration mill or the like. Shape powder). At this time, in order to process each particle independently while preventing aggregation and bonding of the particles, it is preferable to add a fatty acid such as stearic acid or an auxiliary agent such as a surfactant.
And the copper powder which carried out such shape processing can also be utilized, and the original powder which is not shape-processed and this can also be mixed and utilized.
本銅粉は、例えば樹脂硬化型導電性ペースト及び焼成型導電性ペーストのいずれに用いる導電フィラーとしても好適である。
よって、例えばエポキシ樹脂等の熱硬化性樹脂からなる有機バインダーに本銅粉を配合して樹脂硬化型導電性ペーストを調製することもできるし、また、有機ビヒクル中に本銅粉を配合して焼成型導電性ペーストを調製することもできる。 <Application>
The copper powder is suitable as a conductive filler used for, for example, any of a resin curable conductive paste and a fired conductive paste.
Therefore, for example, the present copper powder can be blended with an organic binder made of a thermosetting resin such as an epoxy resin to prepare a resin curable conductive paste, or the present copper powder can be blended into an organic vehicle. A fired conductive paste can also be prepared.
本明細書において「X~Y」(X,Yは任意の数字)と表現する場合、特にことわらない限り「X以上Y以下」の意と共に、「好ましくはXより大きい」或いは「好ましくはYより小さい」の意も包含する。
また、「X以上」(Xは任意の数字)或いは「Y以下」(Yは任意の数字)と表現した場合、「Xより大きいことが好ましい」或いは「Y未満であることが好ましい」旨の意図も包含する。 <Explanation of words>
In the present specification, when expressed as “X to Y” (X and Y are arbitrary numbers), “X is preferably greater than X” or “preferably Y”, with the meaning of “X to Y” unless otherwise specified. It also includes the meaning of “smaller”.
In addition, when expressed as “X or more” (X is an arbitrary number) or “Y or less” (Y is an arbitrary number), it is “preferably greater than X” or “preferably less than Y”. Includes intentions.
実施例および比較例で得られた銅粉に関して、以下に示す方法で諸特性を評価した。 Hereinafter, the present invention will be further described in detail based on the following examples and comparative examples.
With respect to the copper powder obtained in the examples and comparative examples, various properties were evaluated by the following methods.
試料を酸で溶解し、ICPにて分析した。 (1) Element content Samples were dissolved with acid and analyzed by ICP.
酸素・窒素分析装置(堀場製作所株式会社製「EMGA-520(型番)」)を用いて銅粉(サンプル)の酸素濃度(初期酸素濃度ともいう)を分析した。 (2) Oxygen concentration The oxygen concentration (also referred to as initial oxygen concentration) of the copper powder (sample) was analyzed using an oxygen / nitrogen analyzer (“EMGA-520 (model number)” manufactured by Horiba, Ltd.).
銅粉(サンプル)0.2gを純水100ml中に入れて超音波を照射して(3分間)分散させた後、粒度分布測定装置(日機装株式会社製「マイクロトラック(商品名)FRA(型番)」)により、体積累積粒径D50を測定した。 (3) Particle size distribution After putting 0.2g of copper powder (sample) in 100ml of pure water and irradiating with ultrasonic waves (3 minutes), the particle size distribution measuring device ("MICROTRACK" manufactured by Nikkiso Co., Ltd.) Name) FRA (model number) ”), volume cumulative particle size D50 was measured.
ユアサアイオニクス(株)製のモノソーブ(商品名)を用いて、JIS R 1626-1996(ファインセラミックス粉体の気体吸着BET法による比表面積の測定方法)の「6.2流動法の(3.5)一点法」に準拠して、BET比表面積(SSA)の測定を行った。その際、キャリアガスであるヘリウムと、吸着質ガスである窒素の混合ガスを使用した。 (4) BET specific surface area (SSA)
Using monosorb (trade name) manufactured by Yuasa Ionics Co., Ltd., JIS R 1626-1996 (Method of measuring specific surface area of fine ceramic powder by gas adsorption BET method), “6.2 flow method (3. The BET specific surface area (SSA) was measured according to “5) One-point method”. At that time, a mixed gas of helium as a carrier gas and nitrogen as an adsorbate gas was used.
セイコーインスツルメンツ社製の熱機械分析装置(TMA装置)であるTMA/SS6000を用いて焼結開始温度を調べた。
焼結性に関しては、P(リン)を含有した銅よりも適当に焼結が遅れる、すなわちP(リン)を含有した銅の焼結開始温度(490℃前後)よりも焼結開始温度が適当に高い方が本発明の銅粉においては好ましい。そのため、本実施例での「焼結性の評価」は、500~900℃の範囲内のものを「○」、中でも低温領域の500~550℃の範囲のものを「◎」、500~900℃の範囲外のものを「×」と評価した。 (5) Evaluation of sintering start temperature and sinterability The sintering start temperature was examined using TMA / SS6000 which is a thermomechanical analyzer (TMA apparatus) manufactured by Seiko Instruments Inc.
With regard to sinterability, sintering is delayed more appropriately than copper containing P (phosphorus), that is, the sintering start temperature is more appropriate than the sintering start temperature (around 490 ° C.) of copper containing P (phosphorus). Higher is preferable in the copper powder of the present invention. Therefore, the “evaluation of sinterability” in this example is “◯” in the range of 500 to 900 ° C., particularly “◎” in the range of 500 to 550 ° C. in the low temperature region, and 500 to 900. The thing outside the range of ° C. was evaluated as “x”.
電気銅(銅純度:Cu99.95%)を溶解した溶湯(1350℃)に、純金属としてのSi、さらには銅-りんの母合金(P15wt%)を添加して充分に攪拌混合して100kgの溶湯を作製した。
次いで、水アトマイズ装置におけるタンディッシュ中に上記溶湯100kgを注入し(保持温度1300℃)、タンディッシュ底部のノズル(口径5mm)から溶湯を落下させながら(流量5kg/min)、フルコーン型のノズル(口径26mm)の噴射孔から水を逆円錐状の水流形状のなるように上記溶湯にジェット噴射(水圧100MPa、水量350L/min)して水アトマイズすることにより銅粉を製造した。
次に、得られた銅粉を、分級装置(日清エンジニアリング株式会社製「ターボクラシファイアー(商品名)TC-25(型番)」により、分級して銅粉(サンプル)を得た。 <Sample preparation: Examples and Comparative Examples>
100 kg of molten copper (copper purity: Cu 99.95%) melted (1350 ° C) with Si as a pure metal and further a copper-phosphorus mother alloy (P15 wt%) mixed thoroughly and mixed. A molten metal was prepared.
Next, 100 kg of the molten metal was poured into the tundish in the water atomizer (holding temperature 1300 ° C.), and the molten metal was dropped from the nozzle (caliber 5 mm) at the bottom of the tundish (flow rate 5 kg / min). Copper powder was manufactured by jetting water (water pressure: 100 MPa, water amount: 350 L / min) into the molten metal so as to form an inverted conical water flow shape from an injection hole having a diameter of 26 mm).
Next, the obtained copper powder was classified by a classifier (“Turbo Classifier (trade name) TC-25 (model number)” manufactured by Nissin Engineering Co., Ltd.) to obtain a copper powder (sample).
また、実施例6-7で得られた銅粉を電子顕微鏡などで観察し分析した結果、ほとんどがフレーク状粒子であり、銅粉粒子表面から深さ10nmにおけるSi濃度に比べて、表面から深さ2nmにおけるSi濃度が高く、Siが表面層に濃化していることが分かった。 As a result of observing and analyzing the copper powder obtained in Example 1-5 with an electron microscope or the like, most of them were spherical particles, and compared with the Si concentration at a depth of 10 nm from the surface of the copper powder particles, the depth at a depth of 2 nm from the surface. It was found that the Si concentration was high and Si was concentrated in the surface layer.
Moreover, as a result of observing and analyzing the copper powder obtained in Example 6-7 with an electron microscope or the like, most were flaky particles, and the depth from the surface was larger than the Si concentration at a depth of 10 nm from the surface of the copper powder particles. It was found that the Si concentration at 2 nm was high, and Si was concentrated in the surface layer.
また、他の試験により、粒径が小さければ、焼結開始温度が低下する傾向があることが確認されている。しかし、Si(ケイ素)濃度と粒径の何れかを規定するだけでは、焼結開始温度を制御できないことが確認された。その一方、Si濃度とD50の積(Si濃度×D50)を基準値として検討したところ、焼結開始温度を500~900℃の範囲で制御できることが判明した。かかる観点から、本銅粉のSi濃度×D50は、3.50以下であることが重要であり、好ましくは0.001~3.40、特に0.005~3.00、中でも特に0.01~2.80であるのがさらによいと考えることができる。 Comparing the examples and comparative examples, when Si (silicon) is added to copper powder containing P (phosphorus), the Si (silicon) concentration is in the range of 0.01 atm% or more and less than 1.2 atm%, There was a tendency to increase the sintering start temperature by increasing the Si concentration. However, from the viewpoint of sinterability, since Examples 1 and 2 are particularly excellent, it can be considered that the Si (silicon) concentration is preferably less than 0.10 atm% from this viewpoint.
Further, it has been confirmed by other tests that if the particle size is small, the sintering start temperature tends to decrease. However, it has been confirmed that the sintering start temperature cannot be controlled only by defining either the Si (silicon) concentration or the particle size. On the other hand, when the product of Si concentration and D50 (Si concentration × D50) was studied as a reference value, it was found that the sintering start temperature could be controlled in the range of 500 to 900 ° C. From this viewpoint, it is important that the Si concentration x D50 of the copper powder is 3.50 or less, preferably 0.001 to 3.40, particularly 0.005 to 3.00, and particularly 0.01 It can be considered that ˜2.80 is even better.
また、このような効果は、P(りん)濃度には影響されないことが確かめられている。P(りん)濃度は、微粒子化や耐酸化性に影響するため、P(りん)の含有量は0.01~0.3atm%の割合で含有するのが好ましいと考えることができる。
In the embodiment, the value of Si concentration × D50 is changed by fixing D50 and changing the Si concentration. However, the value of Si concentration × D50 is changed by changing D50 in the range of about 0.1 μm to 10 μm. The same effect can be obtained even if the value is changed.
Further, it has been confirmed that such an effect is not influenced by the P (phosphorus) concentration. Since the P (phosphorus) concentration affects the micronization and oxidation resistance, it can be considered that the P (phosphorus) content is preferably 0.01 to 0.3 atm%.
Claims (8)
- Si(ケイ素)及びP(リン)を含有する導電性ペースト用銅粉であって、
Si濃度が0.01atm%以上1.2atm%未満であり、且つ、当該Si濃度(atm%)と、レーザー回折散乱式粒度分布測定法により測定して得られる体積基準粒度分布によるD50(μm)との積によって算出されるSi換算量(Si濃度×D50)が3.50以下であることを特徴とする導電性ペースト用銅粉。 A copper powder for conductive paste containing Si (silicon) and P (phosphorus),
Si concentration is 0.01 atm% or more and less than 1.2 atm%, and D50 (μm) based on the Si concentration (atm%) and a volume-based particle size distribution obtained by measurement by a laser diffraction scattering particle size distribution measurement method. A copper powder for conductive paste, characterized in that the Si equivalent amount (Si concentration × D50) calculated by the product is 3.50 or less. - 銅粉粒子表面から深さ10nmにおけるSi濃度に比べて、表面から深さ2nmにおけるSi濃度が高く、Siが表面層に濃化してなる銅粉粒子を主材としてなることを特徴とする請求項1に記載の導電性ペースト用銅粉。 The Si concentration at a depth of 2 nm from the surface is higher than the Si concentration at a depth of 10 nm from the surface of the copper powder particles, and the main material is copper powder particles formed by concentration of Si in the surface layer. The copper powder for conductive pastes according to 1.
- Si濃度を0.01atm%以上1.2atm%未満の範囲で調整することにより、 焼結開始温度を500~900℃の範囲で調整することができることを特徴とする請求項1又は2に記載の導電性ペースト用銅粉。 The sintering start temperature can be adjusted in a range of 500 to 900 ° C by adjusting the Si concentration in a range of 0.01 atm% or more and less than 1.2 atm%. Copper powder for conductive paste.
- 酸素濃度が800ppm~5000ppmであることを特徴とする請求項1~3の何れかに記載の導電性ペースト用銅粉。 The copper powder for conductive paste according to any one of claims 1 to 3, wherein the oxygen concentration is 800 ppm to 5000 ppm.
- P(りん)の含有量が0.01~0.3atm%であることを特徴とする請求項1~4の何れかに記載の導電性ペースト用銅粉。 5. The copper powder for conductive paste according to claim 1, wherein the content of P (phosphorus) is 0.01 to 0.3 atm%.
- 水アトマイズ法により製造されたものであることを特徴とする請求項1~5の何れかに記載の導電性ペースト用銅粉。 The copper powder for conductive paste according to any one of claims 1 to 5, wherein the copper powder is produced by a water atomization method.
- 請求項1~6の何れかに記載の銅粉を、形状加工処理してなる導電性ペースト用銅粉。 A copper powder for conductive paste obtained by subjecting the copper powder according to any one of claims 1 to 6 to shape processing.
- 請求項1~7の何れかに記載の導電性ペースト用銅粉を含有することを特徴とする導電性ペースト。
A conductive paste comprising the copper powder for conductive paste according to any one of claims 1 to 7.
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Cited By (6)
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EP2851907A4 (en) * | 2012-05-18 | 2016-05-25 | Material Concept Inc | Conductive paste, method for forming wiring, electronic component, and silicon solar cell |
CN105834418A (en) * | 2016-03-17 | 2016-08-10 | 西安工程大学 | Processing method for ethyl cellulose microcapsules of copper powder in electronic slurry |
CN107018624A (en) * | 2016-01-04 | 2017-08-04 | Jx金属株式会社 | Surface treatment copper foil |
EP3345696A4 (en) * | 2015-09-03 | 2019-03-20 | Dowa Electronics Materials Co., Ltd. | Phosphorus-containing copper powder and method for producing same |
CN110578070A (en) * | 2019-10-30 | 2019-12-17 | 吉林大学 | Method for improving oxidation resistance of copper by using authigenic non-metallic oxide composite film |
US20200122229A1 (en) * | 2017-08-21 | 2020-04-23 | Jx Nippon Mining & Metals Corporation | Copper alloy powder for lamination shaping, lamination shaped product production method, and lamination shaped product |
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JP2004263205A (en) * | 2003-01-31 | 2004-09-24 | Toho Titanium Co Ltd | Metallic impalpable powder, manufacturing method therefor, and conductive paste using the metallic impalpable powder |
JP2009079269A (en) * | 2007-09-26 | 2009-04-16 | Dowa Electronics Materials Co Ltd | Copper powder for electroconductive paste, production method therefor and electroconductive paste |
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EP2851907A4 (en) * | 2012-05-18 | 2016-05-25 | Material Concept Inc | Conductive paste, method for forming wiring, electronic component, and silicon solar cell |
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EP3345696A4 (en) * | 2015-09-03 | 2019-03-20 | Dowa Electronics Materials Co., Ltd. | Phosphorus-containing copper powder and method for producing same |
US10773311B2 (en) | 2015-09-03 | 2020-09-15 | Dowa Electronics Materials Co., Ltd. | Phosphorus-containing copper powder and method for producing the same |
CN107018624A (en) * | 2016-01-04 | 2017-08-04 | Jx金属株式会社 | Surface treatment copper foil |
CN105834418A (en) * | 2016-03-17 | 2016-08-10 | 西安工程大学 | Processing method for ethyl cellulose microcapsules of copper powder in electronic slurry |
US20200122229A1 (en) * | 2017-08-21 | 2020-04-23 | Jx Nippon Mining & Metals Corporation | Copper alloy powder for lamination shaping, lamination shaped product production method, and lamination shaped product |
CN110578070A (en) * | 2019-10-30 | 2019-12-17 | 吉林大学 | Method for improving oxidation resistance of copper by using authigenic non-metallic oxide composite film |
CN110578070B (en) * | 2019-10-30 | 2021-04-13 | 吉林大学 | Method for improving oxidation resistance of copper by using authigenic non-metallic oxide composite film |
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TWI432588B (en) | 2014-04-01 |
JP5932638B2 (en) | 2016-06-08 |
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JPWO2011145378A1 (en) | 2013-07-22 |
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